Haibin Pan

Enhancing both selectivity and coking-resistance of a single-atom Pd1/C3N4 catalyst for acetylene hydrogenation

Selective hydrogenation is an important industrial catalytic process in chemical upgrading, where Pd-based catalysts are widely used because of their high hydrogenation activities. However, poor selectivity and short catalyst lifetime because of heavy coke formation have been major concerns. In this work, atomically dispersed Pd atoms were successfully synthesized on graphitic carbon nitride (g-C3N4) using atomic layer deposition. Aberration-corrected high-angle annular dark-field scanning transmission electron microscopy (HAADF-STEM) confirmed the dominant presence of isolated Pd atoms without Pd nanoparticle (NP) formation. During selective hydrogenation of acetylene in excess ethylene, the g-C3N4-supported Pd NP catalysts had strikingly higher ethylene selectivities than the conventional Pd/Al2O3 and Pd/SiO2 catalysts. In-situ X-ray photoemission spectroscopy revealed that the considerable charge transfer from the Pd NPs to g-C3N4 likely plays an important role in the catalytic performance enhancement. More impressively, the single-atom Pd1/C3N4 catalyst exhibited both higher ethylene selectivity and higher coking resistance. Our work demonstrates that the single-atom Pd catalyst is a promising candidate for improving both selectivity and coking-resistance in hydrogenation reactions.

Interaction of Au with thin ZrO2 films: influence of ZrO2 morphology on the adsorption and thermal stability of Au nanoparticles.

The model catalysts of ZrO(2)-supported Au nanoparticles have been prepared by deposition of Au atoms onto the surfaces of thin ZrO(2) films with different morphologies. The adsorption and thermal stability of Au nanoparticles on thin ZrO(2) films have been investigated using synchrotron radiation photoemission spectroscopy (SRPES) and X-ray photoelectron spectroscopy (XPS). The thin ZrO(2) films were prepared by two different methods, giving rise to different morphologies. The first method utilized wet chemical impregnation to synthesize the thin ZrO(2) film through the procedure of first spin-coating a zirconium ethoxide (Zr(OC(2)H(5))(4)) precursor onto a SiO(2)/Si(100) substrate at room temperature followed by calcination at 773 K for 12 h. Scanning electron microscopy (SEM) investigations indicate that highly porous sponge-like nanostructures were obtained in this case. The second method was epitaxial growth of a ZrO(2)(111) film through vacuum evaporation of Zr metal onto Pt(111) in 1 × 10(-6) Torr of oxygen at 550 K followed by annealing at 1000 K. The structural analysis with low energy electron diffraction (LEED) of this film exhibits good long-range ordering. It has been found that Au forms smaller particles on the porous ZrO(2) film as compared to those on the ordered ZrO(2)(111) film at a given coverage. Thermal annealing experiments demonstrate that Au particles are more thermally stable on the porous ZrO(2) surface than on the ZrO(2)(111) surface, although on both surfaces, Au particles experience significant sintering at elevated temperatures. In addition, by annealing the surfaces to 1100 K, Au particles desorb completely from ZrO(2)(111) but not from porous ZrO(2). The enhanced thermal stability for Au on porous ZrO(2) can be attributed to the stronger interaction of the adsorbed Au with the defects and the hindered migration or coalescence resulting from the porous structures.

Interaction of oxygen with samarium on Al2O3 thin film grown on Ni3Al(111)

The interaction between oxygen and samarium (Sm) on the well-ordered thin Al2O3 film grown on Ni3Al(111) has been investigated by X-ray photoelectron spectroscopy and synchrotron radiation photoemission spectroscopy. At Sm coverage higher than one monolayer, exposure of oxygen to the Sm films at room temperature leads to the formation of both samarium peroxide (O2(2-)) states and regular samarium oxide (O(2-)) states. By contrast, when exposing O2 to Sm film less than one monolayer on Al2O3, no O2(2-) can be observed. Upon heating to higher temperatures, these metastable O2(2-) states dissociate, supplying active O atoms which can diffuse through the Al2O3 thin film to further oxidize the underlying Ni3Al(111) substrate, leading to the significant increase of the Al2O3 thin film thickness. Therefore, it can be concluded that Sm, presumably in its peroxide form, acts as a catalyst for the further oxidation of the Ni3Al substrate by supplying the active oxygen species at elevated temperatures.

Growth and Electronic Properties of Ag Nanoparticles on Reduced CeO2?x(111) Films

Ag nanoparticles grown on reduced CeO2−x thin films have been studied by X-ray photoelectron spectroscopy and resonant photoelectron spectroscopy of the valence band to understand the effect of oxygen vacancies in the CeO2−x thin films on the growth and interfacial electronic properties of Ag. Ag grows as three-dimensional particles on the CeO2−x(111) surface at 300 K. Compared to the fully oxidized ceria substrate surface, Ag favors the growth of smaller particles with a larger particle density on the reduced ceria substrate surface, which can be attributed to the nucleation of Ag on oxygen vacancies. The binding energy of Ag3d increases when the Ag particle size decreases, which is mainly attributed to the final-state screening. The interfacial interaction between Ag and CeO2−x(111) is weak. The resonant enhancement of the 4f level of Ce3+ species in RPES indicates a partial Ce4+→Ce3+ reduction after Ag deposited on reduced ceria surface. The sintering temperature of Ag on CeO1.85(111) surface during annealing is a little higher than that of Ag on CeO2(111) surface, indicating that Ag nanoparticles are more stable on the reduced ceria surface.

Grain boundaries modulating active sites in RhCo porous nanospheres for efficient CO 2 hydrogenation

Designing active sites and engineering electronic properties of heterogeneous catalysts are both promising strategies that can be employed to enhance the catalytic activity for CO2 hydrogenation. Herein, we report RhCo porous nanospheres with a high density of accessible grain boundaries as active sites for improved catalytic performance in the hydrogenation of CO2 to methanol. The porous nanosphere morphological feature allows for a high population of grain boundaries to be accessible to the reactants, thereby providing sufficient active sites for the catalytic reaction. Moreover, in-situ X-ray photoelectron spectroscope (XPS) results revealed the creation of negatively charged Rh surface atoms that promoted the activation of CO2 to generate CO2δ– and methoxy intermediates. The obtained RhCo porous nanospheres exhibited remarkable low-temperature catalytic activity with a turnover frequency (TOFRh) of 612 h–1, which was 6.1 and 2.5 times higher than that of Rh/C and RhCo nanoparticles, respectively. This work not only develops an efficient catalyst for CO2 hydrogenation, but also demonstrates a potential approach for the modulation of active sites and electronic properties.